Process for dyeing woolen textiles with metal complex azo dyestuffs



United States Patent 3,157,458 PRQCESS FGR DYEING WQGLEN TEXTILES WITH IVIETAL COMPLEX A20 DYESTUFFS Timothy Leslie Dawson and John Glover Graham, Manchester, England, assignors to Imperial Chemical Industries Limited, London, England, a corporation of Great Britain No Drawing. Filed May 4, 1962, Ser. No. 192,340 Claims priority, appiicatien Great Britain, May 10, 1961, 16,999/61 2 Claims. (Cl. 8-43) This invention relates to a dyeing process and more particularly it relates to a process for dyeing woollen textile materials.

According to the invention there is provided a process for dyeing Woollen textile materials which comprises treating the said textile materials with an aqueous solution containing a reactive premetallised azo-dyestuff, as hereinafter defined, an anionic surface-active agent and a condensate of ethylene oxide with an aliphatic amine.

The process of the invention may be conveniently brought about by immersing the woollen textile materials in a dyebath comprising an aqueous solution of one or more of the reactive premetallised dyestuffs, an anionic surface-active agent and a condensate of ethylene oxide with an aliphatic amine, heating the dyebath for a period at a suitable temperature, for example at a temperature between 80" and 110 C., and thereafter removing the dyed woollen textile materials from the dyebath, and finally drying the textile materials. If desired the dyed textile materials can be rinsed in water before being dried out, in general, this is not essential as little or no dyestufi is removed from the dyed textile materials by this rinsing treatment.

The condensates of ethylene oxide with aliphatic amines used in the process of the invention are preferably the condensates of ethylene oxide with primary aliphatic amines, in particular with primary aliphatic amines which contain from 15 to 30 carbon atoms. As examples of such aliphatic amines there may be mentioned octadecylamine, cetylamine, oleylamine and behenylamine.

The said condensates of ethylene oxide with aliphatic amines are condensates of at least one molecular proportion, and preferably between and 40 molecular proportions, of ethylene oxide with one molecular proportion of the aliphatic amine. As specific examples of such condensates, which may be obtained as described in British specification No. 380,851, there may be mentioned the condensates of 19 molecular proportions of ethylene oxide with one molecular proportion of octadecylamine; the condensate of molecular proportions of ethylene oxide with one molecular proportion of octadecylamine; the condensate of 40 molecular proportions of ethylene oxide with one molecular proportion of octadecylarnine; the condensate of 20 molecular proportions of ethylene oxide with one molecular proportion of behenylamine; the condensate of 20 molecular proportions of ethylene oxide with one molecular proportion of cetylamine.

The anionic surface-active agents used in the process I.

3,157,458 Patented Nov. 17., 1964 sulphonic acid, and the dioctylester of sodium sulphosuccinate.

The amount of the anionic surface-active agent used in the process of the invention should be between 0.01% and 2%, and preferably between 0.1% and 0.5%, based on the weight of the woollen textile materials. If desired mixtures of 2 or more anionic surface-active agents can be used in the process of the invention.

The amount of the condensate of ethylene oxide with an aliphatic amine used in the process of the invention should be between 0.1% and 5%, and preferably between 0.3% and 1.5%, based on the weight of the wool. If desired mixtures of 2 or more condensates of ethylene oxide with aliphatic amines can be used in the process of the invention.

If desired the dyebath can also contain substances which are commonly used in the dyeing of woollen textile materials. As examples of such substances there may be mentioned mineral acids, such as sulphuric and phosphoric acids, organic acids such as formic acid or acetic acid, or salts thereof such as sodium dihydrogen phos phate, disodium hydrogen phosphate, ammonium acetate, ammonium sulphate or sodium sulphate. Mixtures of the above salts and acids may also be present, such as acetic acid and sodium acetate.

By the term reactive premetallised azo dyestufi there is meant a 1:2-chromium or cobalt complex of an azo dyestufi? which contains (a) not more than one sulphonic acid or non-chelated carboxylic acid group, or a salt thereof, and (b) at least one reactive halogen atom or reactive group, that is to say a halogen atom or group which is capable of reacting with the woollen textile material through a chemical bond. Examples of classes of such reactive premetallised dyestufis include 1:2-chromium or cobalt complexes of azo dyestuffs containing at least one 4:6-dihalogeno-1:3z5-triazin-2-ylamino group; 1:2-chromium or cobalt complexes of azo dyestulfs containing at least one 4-halogeno-1z3tS-triazin-2-ylamino group, wherein the carbon atom in the 6-position of the triazine ring can be substituted by, for example, a lower alkyl radical, a lower alkoxy radical, a hydroxy group, a mercapto group, a substituted mercapto group, a sulphonic acid group, a thiocyano group, a quaternary ammonium group, or an amino or substituted amino group; 1:2-chromium or cobalt complexes of azo dyestufls containing at least one mono-, dior tri-halogeno-pyrimidylamino group; 1:2-chrorninum or cobalt complexes of azo dyestuffs containing at least one halogenoalkylsulphamyl group, in particular a B-halogenoethylsulphamyl group, or at least one 'y-halogeno-fl-hydroxypropylsulphamyl group; 1:2-chromium or cobalt complexes of azo dyestuffs containing at least one [i-chloroethylsulphonyl, 'y-chloroor -hydroxy-a:B-propenylsulphonyl, or vinylsulphonyl group, 1:2-chromium or cobalt complexes of azo dyestuffs containing at least one acryloylamino or halogenoacrylamino group, 1:2-chrornium or cobalt complexes of azo dyestulfs containing at least one halogenoacylamino group such as halogenoacetylamino or B-halogenopropionylarnino groups; and 1:2-chromium or cobalt complexes of azo dyestuffs containing at least one B-(alkyl or aryl)sulphonyloxyethylsulphone or i-acyloxyethylsulphonyl group.

In the above classes halogeno denotes bromo and preferably chloro, alkyl preferably denotes lower alkyl, and aryl preferably denotes a monocyclic aryl radical. The term lower alkyl is used to denote a low molecular weight alkyl radical, in particular an alkyl radical containing from 1 to 6 carbon atoms.

Reactive premetallised azo dyestuffs which can be used in the process of the invention may themselves be obtained by treating with an agent yielding chromium or 3 cobalt one or two diflerent metallisable azo compounds which contain at least one reactive group, or alternatively by introducing a reactive group or'groups into a preformed 1:2-chromium or cobalt complex of'an azo compound, for example by treating a 1:2-chromium or cobalt complex of an azo compound containing at least' one amino group with an acylating agent which contains the desired reactive group, such as dior tri-halogeno-1z3z5- triazines, tri or tetra-halogenopyrimidines and acid chlorides or anhydrides of unsaturated aliphatic carboxylic acids or of halogenoaliphatic carboxylic acids.

Specific examples of reactive premetallised azo dyestuiis which can be used in the process of the invention are described in British specifications Nos. 787,986 and 876,718 and in Belgian specifications Nos. 577,140, 579,- 968, 591,397, 592,883, 592,884, 609,774, 609,775 and 610,138.

It is however preferred that the reactive premetallised azo dyestutfs used in the process of the invention are free from asulphonic acid or non-chelated carboxylic acid group.

As examples of woollen textile materials which may be dyed by the process of the invention there may be mentioned loose Wool, combed wool tops (slubbing), and particularly woollen yarn (in hank or cheese form) and piece goods (woven or knitted).

By the process of the invention woollen textile materials are dyed in level shades which possess excellent fastness to light, to wet treatments such as washing, potting and acid-cross dyeing, and to rubbing. The dyeings so obtained are also free from the fibre to fibre unlevelness known as skitteriness.

The invention is illustrated but not limit by the following examples in which the parts and percentages'are by weight.

' 'Example 1 20 parts of worsted yarn are immersed in a dyebath comprising a solution of 0.2 part of the 1:2-chromium complex of 1-(2'- hydroxy 4 sulphamylphenylazo) -8- acryloylamino-Z-naphthol (which is described in Example 13 of Belgian specification No. 591,397), 0.05 part of the fastness to Wet treatments to a dyeing obtained as dedinaphthylmethane disulphonic acid was'ornitted from the dyebath.

Example 2 In place of the 0.2 part'of the dyestuif used in Example 1 there is used 1.0 part of the mixed 1:2-chromium complex of l-phenyl 3 methyl-4-(2'-hydroxy-5-niIIophenylazo)-5-pyrazolone and 1-(4'-acryloylaminophenyl)-3-methyl 4 (2'-hydroxy 5' sulphophenylazo)-5- pyrazolone whereby the yarn is dyed a reddish-orange shade which is fast to wet treatments, and the dyeing so obtained is superior in respect of rubbing fastness and scribed above except that the 0.5 part of the disodium salt of dinaphthylmethane was omitted from the dyebath. a

The dyestuif used in the above example may be obtained by stirring a mixture of equimolecular proportions of 1-(4'-acryloy1aminophenyl)-3 methyl-4-(2'-hydroxy- 5'-sulphophenylazo)-5-pyrazolone and the 1: l-chromiuin complex of 1,-phenyl- 3 methyl-4-(2-hydroxy-5' nitrophenylazo)-5-pyrazolone in a 0.5% aqueous solution of sodium carbonate for 2 hours at 95 to 100 C., cooling to 20 0., adding sodium chloride and filtering oil th precipitated dyestuif.

Example 3 In place of the 0.05 part of the disodium salt of dinaphthylmethane disulphonic acid used in Examples 1 and 2 there is used 0.02 part ofsodium tiiisopropylnaphthalene sulphonate or 0.02 part of sodium oleyl sulphate or 0.04 part of sulphonated sperm oil, when similar results are obtained.

Examples 4 to 12 Example Dyestufi Parts Shade used 4 The 1:2chromium complex of 1-(2-hydroxy-4-sulphamy1phenylazo-8- 0.2 Bluish grey.

(B-chloro-propionylamino)-2 naphthol.

5 'The 1:2-chro1nium complex of 1-(2-hydroxy-4-sulphamylphenylazo-S- 0.2 Do.

chloro-acetylamino-2naphthol.

6 The 1:2-chromium complex of 1-(5--y-chloro-B-hy lroxypropylsulphonyl- O. 25 Dull violet.

Z-methoxyphenylazc)-2-naphthol.

7 The 1:2-ehrornium complex of 1-(S y-hydroxyprop-l-enylsulph0nyl-2- 0.2 Do.

methoxy-phenylazo)-2-naphtho1.

8 The 1:2-c0ba1t complex of l-phenyl-4-(2-hydwiry-5-6-benzoyloxyethyl- 0. 2 Dull bluish sulplionylphenylazo)-3-methyl-5-pyrazolone. red.

9 The lz2-chromium complex of 8acetylamino-l-(5-vinylsulphonyl-2- 0, 25 Bluish grey.

hydroxyphenylazo)-2-naphthol.

10 The mixed 1:2-chromium complex of 1:2-dihydroxy-2:1-azonaphtha 0. 6 Bluish black.

lene-4-sulphonie acid and 2-(4-sulphamyl-2-hydroxyphenylazo)4- acryloylamino-l-naphthol.

11 The mixed 1:2-chromiun1 complex of l-(4-sulph01-naphthyl)-4-(Z- 0.3 Brown.

hydroxy-S -B methy1su1phon yloxyethylsulphonylphenylazo) 3 methyl W S-pyrazolone and 1(4 -sulphamyl-2-hydroxylpheuylazo) -2-naphthol.

12; The mixed 1:2-chromium complex of l-(5-vinylsulphonyl-2-hydr0xy- 0.2 Dull bluish phenylazo)-5:6:7:S-tetah drQ-Zhydroxynapthalene-Ii-sulphonic acid violet.

and3-sulphamyl-2-(5chloro-2-hy lr0xyphenylazo)-2-naphth01.

disodium salt of dinaphthylmethane disulphonic acid, 0.1. part of a condensate of 19 molecular proportions of ethylene oxide with one molecular proportion of octadecylamine, and 0.6 part of ammonium acetate in 1000 parts of water. The dyebath is then heated to 100 C. during 30 minutes, and maintained at 100 C. for 1 hour. The dyed yarn is then removed from the dyebath, and dried.

The yarn is thereby dyed a grey shade which is fast to light and to wet treatments, and the dyeing so obtained is superior in'respect of rubbing fastness and fastness to wet treatments to a dyeing which wasobtained as described above except that the 0.05 part of the disodium salt of Example 13 v A mixture of 0.2 part of the dyestuif used in Example sate of 19 molecularproportions of ethylene oxide'with one molecular proportion of octadecylamine, 0.05 part of the disodium salt of dinaphthylmethane.disulphonieacid and 1.0 part of ammonium dihydrogen phosphate containedin a circulating liquor;cheese dyeing machine.

'20 parts of worsted yarn, wound in cheese form, are

H hen placed in the dyebath, and, with the liquor circulating through the cheese, the temperature ofthe dyebath is raised to 85 C. The dye solution, prepared as described above is then added to the dyebath, the temperature of which is then raised to 100 C. in 15 minutes, dyeing being continued at the boil for a further 45 minutes. The dye liquor is then drained, and the cheese removed and dried.

The wool yarn is dyed an olive green shade and when portions of the yarn from the outside, centre and inside of the cheese are knitted, the knitted fabric is uniformly coloured and possesses good fastness to rubbing and to wet treatments.

If a second cheese is dyed as described above except that the disodium salt of dinaphthylmethane disulphonic acid is omitted from the dyebath, a fabric knitted from portions of the yarn shoWs variations in shade due to differences in the dyed yarn taken from the outside, centre and inside of the dyed cheese. The knitted fabric is also skittery and possesses inferior fastness to rubbing and to wet treatments compared with the knitting obtained from the yarn dyed as described in the first part of this example. 7

What we claim is:

l. A process for dyeing Woolen textile materials which comprises treating the woolen textile material with an aqueous solution containing:

(l) a member selected from the class consisting of 1:2-

chromium and cobalt complexes of azo dyestufis, free from sulphonic acid and non-chelated carboxylic acid groups, and containing a member selected from the group consisting oi reactive halogen atoms and reactive groups capable of reacting with the woolen textile material in the dyeing reaction to form a chemical bond therein;

(2) an anionic surface-active agent; and

(3) a condensate of ethylene oxide with an aliphatic amine.

2. The process of claim 1, wherein the said condensate of ethylene oxide with an aliphatic amine is the condensate of ethylene oxide with a primary aliphatic amine containing from 15 to carbon atoms.

References Cited by the Examiner UNITED STATES PATENTS 1/63 Buehler et a1 9-54 XR OTHER REFERENCES ABRAHAM H. WINKELSTEIN, Examiner. 

1. A PROCESS FOR DYEING WOOLEN TEXTILE MATERIALS WHICH COMPRISES TREATING THE WOLLEN TEXTILE MATERIAL WITH AN AQUEOUS SOLUTION CONTAINING: (1) A MEMBER SELECTED FROM THE CLASS CONSISTING OF 1:2CHROMIUM AND COBALT COMPLEXES OF AZO DYESTUFFS, FREE FROM SULPHONIC ACID AND NON-CHELATED CARBOXYLIC ACID GROUPS, AND CONTAINING A MEMBER SELECTED FROM THE GROUP CONSISTING OF REACTIVE HALOGEN ATOMS AND REACTIVE GROUPS CAPABLE OF REACTING WITH ATHE WOOLEN TEXTILE MATERIAL IN THE DYEING REACTION TO FORM A CHEMICAL BOND THEREIN; (2) AN ANIONIC SURFACE-ACTIVE AGENT; AND (3) A CONDENSATE OF ETHYLENE OXIDE WITH AN ALIPHATIC AMINE. 